Method for producing triazinyl-substituted oxindoles

ABSTRACT

Process for the preparation of triazinyl-substituted oxindoles of formula (3) 
                         
and salts thereof by reacting an oxindole (1) with a triazine (2) in the presence of a carbonate, a hydroxide, a phosphate or a mixture of two or more of the aforementioned compounds, and also the compounds of formula (3) and salts thereof (3″) and the use of both for producing crop protection agents.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a §371 National Stage Application ofPCT/EP2011/073283, filed Dec. 19, 2011, which claims priority toEuropean Application No. 10196205.8, filed Dec. 21, 2010, and U.S.Provisional Application No. 61/425,349, filed Dec. 21, 2010.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present application relates to improved processes for thepreparation of triazinyl-substituted oxindoles and their use asintermediates for the synthesis of fine chemicals and of activeingredients in the field of agriculture.

2. Description of Related Art

Oxindoles substituted in the 3 position are an important structuralmotif among a series of natural substances and pharmaceuticallyeffective substances. Some of these compounds exhibit biologicalactivity against various pathogens and have e.g. antitumor or anti-HIVproperties (Ding et al., J. Med. Chem. 2006, 49, 3432; Jiang et al.,Bioorg. Med. Chem. Lett. 2006, 16, 2105).

A further subgroup of the oxindoles substituted heteroaromatically inthe 3 position are the 3-triazinyloxindoles(3-(1,3,5-triazin-2-yl)-1,3-dihydro-2H-indol-2-one. The preparation ofthese compounds, referred to by the trivial name of“3-triazinyloxindoles”, is the subject of the present invention.

It is known that a hydrogen bonded to an aromatic, heteroaromatic or toan aliphatic carbon backbone can be exchanged for functionalsubstituents which may likewise be aromatic, heteroaromatic oraliphatic.

In this connection, it is interesting that the reaction conditions forthe substitution of the hydrogen in the 3 position of oxindoles aredifferent depending on the nature of the substituents. Accordingly, thereaction conditions for the exchange for aliphatic, aromatic andheteroaromatic radicals have been researched and developed independentlyof one another.

Standard reactions of the substitution of oxindoles in the 3 positioninclude the exchange of hydrogen for aliphatic substituents (Science ofSynthesis, 10 (2000), p. 600).

The exchange for aromatic substituents in the presence of palladium wasdescribed by Taylor et al. (J. Am. Chem. Soc., 2009, 131, 9900-9901),and also by Altman et al. (J. Am. Chem. Soc. 2008, 130 (29), 9613-9620),and also by Durbin et al. (Org. Lett., 2008, 10 (7), 1413-1415).

The synthesis of substituted oxindoles in which the hydrogen have beenexchanged for heteroaromatic 6-ring substituents has likewise beendescribed. By way of example, mention is made here of the substitutionin the 3 position of N-methyl-oxindole with a substituted pyridazine(Shen et al., Org. Lett., 2006, 8, 1447-1450), the preparation ofsubstituted 3-(quinazolin-4-yl)oxindoles (U.S. Pat. No. 6,265,411), thesubstitution in the 3 position of oxindole with substituted quinazolinesover a solid phase (Hennequin et al., Tetrahedron Lett., 1999, 40,3881-3884), the substitution with substituted pyridines or pyridineN-oxides (e.g. US 2009/291982, WO 2007/89193, WO 2005/27823, WO2003/82853), the preparation of substituted 3-(pyrimidin-4-yl)oxindoles(WO 2006/136606, WO 2003/82853, US 2007/281949) or the preparation ofsubstituted 3-(2H-pyrazolo[3,4-d]pyrimidin-4-yl)oxindoles (US2007/281949).

According to Scheme 1,3-triazinyloxindoles can be obtained by exchanginga hydrogen atom in the 3 position of an optionally substituted oxindole(1) for an optionally substituted triazine (2) which carries a suitableleaving group X, in the presence of a “suitable” base.

In this connection, it is known that the step of deprotonation of theoxindole that is important for the exchange of the hydrogen can beinfluenced in a targeted manner through the choice of substituent R³.

A common feature of the reactions disclosed in the aforementioned priorart is that the oxindole used is firstly deprotonated with a strong baseand then the heterocyclic component, typically as chlorine compound, isadded.

For the purposes of the deprotonation, in the prior art, strong,water-sensitive bases, such as sodium hexamethyldisilazane or lithiumdiisopropylamide (LDA), sodium hydride or lithium hydride, are used.

Disadvantageously, the use of the bases sodium hydride and lithiumhydride leads to the formation of equimolar amounts of elementalhydrogen. Moreover, the solvents used in connection with these baseshave to be laboriously dried prior to being used.

An analogous coupling—analogous to the coupling of oxindoles withquinolines described in WO 2005/061519, in which quinoline N-oxides areused in the presence of acidic anhydride—with triazines of formula (2)is not known.

Scheme 2 summarizes a known process for the preparation of substituted3-triazinyloxindoles. These are characterized in that they carrynitrogen substituent on the triazine ring. The synthesis is disclosed inUS 2004/116388, WO 2002/083654 and WO 2001/025220.

In the reaction according to Scheme 2, a substituted4-chloro-N-phenyl-1,3,5-triazine-2-amine was used as triazine-containingcomponent. The reaction was carried out by deprotonation of the oxindoleused in DMF/THF with sodium hydride, followed by the addition of thetriazine component and subsequent stirring of the reaction mixture at80° C.

Disadvantageously, the achieved yields for this known synthesis are only2.5%, or 7% for the oxindoles unsubstituted on the nitrogen (R²═H), and29% for N-methyl-oxindole (R²=Me).

As well as the very low yields, the disadvantages of the describedprocess are also the use of strong bases such as sodium hydride, whichlead to the formation of equimolar amounts of elemental hydrogen, whichare difficult to handle industrially. Consequently, the describedprocess is not a viable solution for the industrial scale.

In the process, described in US 2004/116388 for the compound with thenumber 380, for the preparation of substituted 3-triazinyloxindoles,only 0.4 equivalents of the triazine component are used per equivalentof the oxindole component. Based on the oxindole component, this canlead merely to a maximum theoretical yield of 40%. An increase in theyield can be achieved through the use of an excess of oxindole. Sincethe oxindole component can, depending on the substitution pattern, bethe somewhat more valuable starting material, this reaction procedureusing a 2.5-fold excess of oxindole on an industrial scale is to beregarded as disadvantageous.

It has already been indicated that the reaction conditions for theexchange of the hydrogen in the 3 position of oxindoles for aliphatic,aromatic and heteroaromatic substituents had to be established in eachcase independently of one another because the type of substituents to beintroduced can heavily influence the reaction.

The same appears to apply in turn to the further branching, i.e. thefurther substitution of these substituents, in particular to the furthersubstitution of the heteroaromatic substituents.

Thus, the prior art describes no industrially suitable synthesis of3-triazinyloxindoles which carry alkyl or alkoxy substituents on thetriazine ring.

The use of the hitherto known preparation processes in the synthesis of3-triazinyloxindoles which carry alkyl or alkoxy substituents on thetriazine ring does not produce satisfactory results on an industrialscale.

For comparison purposes, the conditions, described in the document US2004/116388, in the reaction of 7-fluoro-1,3-dihydro-2H-indol-2-one(example 1 Variant F), or 1,3-dihydro-2H-indol-2-one (Example 2 VariantB) with 2-chloro-4,6-dimethoxy-1,3,5-triazine were used.

In this connection, it was found that the yields achieved, in each casebased on the oxindole component, are only 39% (Example 1 Variant F), oronly 34% (Example 2 Variant B). If these conditions are used in thereaction of the starting materials in an industrially advantageousratio, namely 1 equivalent of the oxindole component with 1.2equivalents of the triazine component, then the yields achieved are 39%(Example 1 Variant G) or 30% (Example 2 Variant C).

In Organic Letters (2010) 2306-2309, in the arylation reactionsdescribed in Table 4, the starting material used in each case is3-phenyloxindole, i.e. an oxindole which carries a phenyl substituent inthe 3 position. This 3-phenyloxindole is arylated with electron-poorchlorobenzene derivatives and 5-halooxazoles in the presence of caesiumcarbonate in the 3 position.

As is known, the acidity of methyl groups or methylene groups is usuallygreatly increased by exchanging a hydrogen substituent for a phenylsubstituent. This leads to a reduced pKa value of the remaining hydrogensubstituent(s) on methyl group or methylene group by several orders ofmagnitude.

In a series of publications, corresponding examples can be found inwhich pKa values of organic or inorganic compounds in water or inorganic solvents such as dimethyl sulfoxide are described. The pKavalues in organic solvents were either measured directly or extrapolatedby means of other methods. For example, in Acc. Chem. Res. 1988, 21, 456in Table II, for 4-methylpyridine, a pKa value of 35 (extrapolated forDMSO) and for 4-benzylpyridine a pKa value of 26.7 (in DMSO) is given.Likewise in Acc. Chem. Res. 1988, 21, 456 in Table II, for(methylsulfanyl)benzene, a pKa value of 42 (extrapolated for DMSO) isgiven, for (benzylsulfanyl)benzene, a pKa value of 30.8 (in DMSO) isgiven, and for diphenylmethyl phenylsulfide, a pKa value of 26.8 (inDMSO) is given. For oxindole, in Acc. Chem. Res. 1988, 21, 456 in TableII, a pKa value of 18.2 (in DMSO) is given.

From the examples given, the increase in acidity of methyl groups ormethylene groups by several orders of magnitude as a result ofexchanging a hydrogen substituent for a phenylsubstituent becomes veryevident.

In the examples of the present application, the starting materials usedwere only oxindoles which carry two hydrogen atoms in the 3 position. InOrganic Letters (2010) 2306-2309, by contrast, 3-phenyloxindoles areused as starting materials. The starting materials therefore differ intheir acidity. Oxindoles which carry two hydrogen atoms in the 3position are less acidic than the 3-phenyloxindole used in OrganicLetters (2010) 2306-2309 in the reactions of Table 4.

It is therefore not surprising that in the literature examples in whicharylation reactions on oxindoles unsubstituted in the 3 position aredescribed, strong bases such as sodium hydride are used. The fact thatalso for oxindoles which carry a substituent in the 3 position whichreduces the acidity in non-aqueous solvents by several orders ofmagnitude, relatively weak bases such as caesium carbonate can be usedfor the deprotonation was to be expected by the person skilled in theart and was confirmed in Organic Letters (2010) 2306-2309.

However, it is surprising to the person skilled in the art that,according to the teaching of the invention, an arylation reaction onoxindoles unsubstituted in the 3 position (oxindoles which have twohydrogens in the 3 position) is possible, contrary to expectations, evenwith relatively weak bases such as potassium carbonate or sodiumhydroxide in good yields.

In order to test the applicability of the conditions described inOrganic Letters (2010) 2306 (Supplement page S-12 General Procedure) forthe arylation of 3-aryloxindoles with electron-poor chlorobenzenederivatives and 5-halooxazoles (Table 4 in Organic Letters (2010) 2306)also when using chlorotriazines, 3-phenyl-1,3-dihydro-2H-indol-2-one wasreacted with 2-chloro-4,6-dimethoxy-1,3,5-triazine in the presence ofcaesium carbonate in N,N-dimethylformamide (see Example 10). Since thereaction proceeded very rapidly even at room temperature, an elevatedtemperature and extended reaction time were dispensed with. The productpresent in the reaction mixture was purified by column chromatography.Structural elucidation by means of 2D-NMR demonstrates that the productobtained, however, is not the desired product arylated in the 3 position(3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-3-phenyl-1,3-dihydro-2H-indol-2-one),but the O-arylated product(2-[(4,6-dimethyoxy-1,3,5-triazin-2-yl)oxy]-3-phenyl-1H-indole).

Afterwards, again for comparison purposes, the conditions for thearylation described in Organic Letters (2010) 2306 (Supplement page S-12General Procedure) were likewise applied while using chlorotriazines,and specifically for the arylation of an oxindole unsubstituted in the 3position. For this purpose, 7-fluoro-1,3-dihydro-2H-indol-2-one wasreacted with 2-chloro-4,6-dimethoxy-1,3,5-triazine in the presence ofcaesium carbonate in N,N-dimethylformamide (Example 1 variant H).However, the title compound arylated in the 3 position with only 22%yield is obtained as reaction product. As main products, polyarylatedproducts were obtained in the isolated solid and also in theconcentrated mother liquor. It was also shown, by means of HPLCanalysis, that the oxindole used as starting material had not completelyfully reacted.

Consequently, the process described in Organic Letters (2010) 2306(Supplement page S-12 General Procedure) is not suitable for producing3-triazinyloxindoles on an industrial scale, at least when2-chloro-4,6-dimethoxy-1,3,5-triazine is used as arylating reagent.

SUMMARY

Against this background, the object of the invention consists in theprovision of an improved process which permits, on an industrial scale,a preparation of 3-triazinyloxindoles that is simplified compared to theknown processes, coupled with improved overall yield.

Surprisingly, it has now been found that the relatively weak basespotassium carbonate or sodium carbonate, and also lithium hydroxide,sodium hydroxide, potassium hydroxide, barium hydroxide ortert-alkylammonium hydroxide, and also potassium phosphate (K₃PO₄),K₂HPO₄ or sodium phosphate or mixtures consisting of at least two of theaforementioned bases, are suitable for achieving the object.

The specified bases have the advantage that they are suitable for use onan industrial scale since they cannot be decomposed particularly in thepresence of water, and also do not produce equimolar amounts of hydrogenand at the same time lead to a significantly improved overall yield.

The object is thus achieved by a process for the preparation ofcompounds of formula (3)

in which

-   R^(1a) to R^(1d), independently of one another, are selected from    the group consisting of hydrogen, fluorine, chlorine, bromine,    iodine, and also from-   (C₁-C₆)-alkyl, where the alkyl radical is branched or unbranched and    is unsubstituted or is substituted by one or more substituents    selected from the group consisting of fluorine, chlorine,    (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,-   (C₃-C₇)-cycloalkyl, where the cycloalkyl radical is unsubstituted or    is substituted by one or more substituents selected from the group    consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkoxy,-   (C₁-C₆)-alkoxy, where the alkoxy radical is branched or unbranched    and is unsubstituted or is substituted by one or more substituents    selected from the group consisting of fluorine, chlorine,    (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,-   (C₃-C₇)-cycloalkoxy, where the cycloalkoxy radical is unsubstituted    or is substituted by one or more substituents selected from the    group consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₁-C₄)-alkoxy,-   (C₁-C₆)-alkylthio, where the alkylthio radical is branched or    unbranched and is unsubstituted or is substituted by one or more    substituents selected from the group consisting of fluorine,    chlorine, (C₁-C₄)-alkyl or (C₁-C₄)-alkoxy,-   (C₃-C₇)-cycloalkylthio, where the cycloalkylthio radical is    unsubstituted or is substituted by one or more substituents selected    from the group consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₁-C₄)-alkoxy, and    -   phenyl or 1-naphthyl or 2-naphthyl or a five- or six-membered        heteroaromatic ring having 1 to 2 heteroatoms, where the        heteroatoms, independently of one another, are selected from the        group consisting of O or N and where the aryl or heteroaryl        radical is unsubstituted or is substituted by one or more        substituents selected from the group consisting of fluorine,        chlorine, bromine, iodine, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or        (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkylthio, and    -   R² is        -   hydrogen,        -   (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or            is substituted by one or more substituents selected from the            group consisting of fluorine, chlorine, (C₁-C₄)-alkoxy or            (C₃-C₇)-cycloalkyl, or        -   benzyl, where the benzyl is unsubstituted or is substituted            by one or more substituents selected from the group            consisting of fluorine, chlorine, bromine, iodine, nitro,            (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl or            (C₁-C₄)-alkylthio and also from COOR^(a), in which R^(a) is            a (C₁-C₄)-alkyl, and —CONR^(b′)R^(b″) or —CONHR^(b″), in            which R^(b′) and R^(b″) are each independently of one            another a (C₁-C₄)-alkyl, where in each case two substituents            on the N atom together optionally form an unsubstituted or            substituted ring,    -   R³ is        -   hydrogen,    -   R⁴ and R⁵, independently of one another, are in each case        hydrogen,        -   (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or            is substituted by one or more substituents selected from the            group consisting of fluorine, chlorine, (C₁-C₄)-alkoxy or            (C₃-C₇)-cycloalkyl,        -   (C₁-C₆)-alkoxy, where the alkoxy radical is branched or            unbranched and is unsubstituted or is substituted by one or            more substituents selected from the group consisting of            fluorine, chlorine, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,    -   where an oxindole (1)

-   -    in which    -   R^(1a) to R^(1d) and R² and R³ are as defined in formula (3), is        reacted in a solvent with a triazine (2)

-   -    in which    -   R⁴ and R⁵ are as defined in formula (3), and    -   X, as leaving group, is Cl, Br, I, alkoxy, alkylsulfonyl,        (alkylsulfonyl)oxy, haloalkylsulfonyl, phenylsulfonyl or        toluene-4-sulfonyl, which comprises carrying out the reaction in        the presence of        -   potassium carbonate or sodium carbonate,        -   lithium hydroxide, sodium hydroxide, potassium hydroxide,            barium hydroxide or tert-alkylammonium hydroxide,        -   potassium phosphate (K₃PO₄), potassium hydrogenphosphate            (K₂HPO₄) or sodium phosphate or        -   in a mixture comprising at least two of the aforementioned            bases.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

Wherever reference is made in this application to an “oxindole”, one ofthe compounds encompassed by formula (1) is intended. The oxindoles (1)used as starting materials

in which the radicals R^(1a) to R^(1d), R² and R³ are as defined above,are known or can be prepared using the processes known to the personskilled in the art. Wherever reference is made in this application to a“triazine” or a “triazine component”, one of the compounds encompassedby formula (2) is intended. The triazines (2) likewise used as startingmaterials

in which R⁴, R⁵ and X are as defined above, are likewise known or can beprepared using processes known to the person skilled in the art.

As regards the compounds according to the invention, the terms usedabove and below are explained in summary. These are familiar to theperson skilled in the art and have in particular the meanings explainedbelow:

The term “halogen” means, for example, fluorine, chlorine, bromine oriodine. If the term is used for a radical, then “halogen” means forexample a fluorine, chlorine, bromine or iodine atom.

Alkyl means a straight-chain or branched open-chain, saturatedhydrocarbon radical.

The expression “(C₁-C₄)-alkyl” is short-hand for alkyl having one to 4carbon atoms corresponding to the stated range for carbon atoms, i.e.encompasses the radicals methyl, ethyl, 1-propyl, 2-propyl, 1-butyl,2-butyl, 2-methylpropyl or tert-butyl. General alkyl radicals with alarger stated range of carbon atoms, e.g. “(C₁-C₆)-alkyl”, accordinglyalso encompass straight-chain or branched alkyl radicals having a largernumber of carbon atoms, i.e. according to the example also the alkylradicals having 5 and 6 carbon atoms.

Cycloalkyl means a carbocyclic, saturated ring system having preferably3-8 ring carbon atoms, e.g. cyclopropyl, cyclobutyl, cyclopentyl orcyclohexyl. In the case of optionally substituted cycloalkyl, cyclicsystems with substituents are encompassed, in which case alsosubstituents with a double bond on the cycloalkyl radical, e.g. analkylidene group such as methylidene, are encompassed.

In the case of optionally substituted cycloalkyl, also polycyclicaliphatic systems are encompassed, such as, for example,bicyclo[1.1.0]butan-1-yl, bicyclo[1.1.0]butan-2-yl,bicyclo[2.1.0]pentan-1-yl, bicyclo[2.1.0]pentan-2-yl,bicyclo[2.1.0]pentan-5-yl, bicyclo[2.2.1]hept-2-yl (norbornyl),adamantan-1-yl and adamantan-2-yl.

In the case of substituted cycloalkyl, also spirocyclic aliphaticsystems are encompassed, such as, for example spiro[2.2]pent-1-yl,spiro[2.3]hex-1-yl, spiro[2.3]hex-4-yl, 3-spiro[2.3]hex-5-yl.

Aryl means a mono-, bi- or polycyclic aromatic system having preferably6 to 14, in particular 6 to 10, ring carbon atoms, for example phenyl,naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.

The term “optionally substituted aryl” also encompasses polycyclicsystems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl,biphenylyl, the bonding site being on the aromatic system.

From the point of view of systematics, aryl is usually also encompassedby the term “optionally substituted phenyl”.

Alkoxy means an alkyl radical bonded via an oxygen atom, alkenyloxymeans an alkenyl radical bonded via an oxygen atom, alkynyloxy means analkynyloxy radical bonded via an oxygen, cycloalkyloxy means acycloalkyl radical bonded via an oxygen atom and cycloalkenyloxy means acycloalkenyl radical bonded via an oxygen atom.

Alkylthio means an alkyl radical bonded via a sulfur atom, alkenylthiomeans an alkenyl radical bonded via a sulfur atom, alkynylthio means analkynyl radical bonded via a sulfur atom, cycloalkylthio means acycloalkyl radical bonded via a sulfur atom and cycloalkenylthio means acycloalkenyl radical bonded via a sulfur atom.

Haloalkyl, haloalkenyl and haloalkynyl mean alkyl, alkenyl or alkynyl,respectively, partially or completely substituted by identical ordifferent halogen atoms, e.g. monohaloalkyl, such as CH₂CH₂Cl, CH₂CH₂F,CHClCH₃, CHFCH₃, CH₂Cl, CH₂F; perhaloalkyl such as CCl₃ or CF₃ orCF₂CF₃; polyhaloalkyl such as CHF₂, CH₂F, CH₂CHFCl, CHCl₂, CF₂CF₂H,CH₂CF₃; haloalkoxy is e.g. OCF₃, OCHF₂, OCH₂F, OCF₂CF₃, OCH₂CF₃ andOCH₂CH₂Cl; the same applies to haloalkenyl and other radicalssubstituted by halogen.

Unless defined otherwise, the definition “is substituted with one ormore radicals” means, independently of one another, one or moreidentical or different radicals where two or more radicals on a cycle asparent body are able to form one or more rings.

Substituted radicals, such as a substituted alkyl, cycloalkyl,cycloalkenyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical,are, for example, a substituted radical derived from the unsubstitutedparent body, where the substituents are, for example, one or more,preferably 1, 2 or 3 radicals from the group halogen, alkoxy, alkylthio,hydroxy, amino, nitro, carboxy or a group equivalent to the carboxygroup, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl,carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such asacylamino, mono- and dialkylamino, trialkylsilyl and optionallysubstituted cycloalkyl, optionally substituted aryl, optionallysubstituted heterocyclyl, where each of the last-mentioned cyclic groupscan also be bonded via heteroatoms or divalent functional groups as inthe case of the specified alkyl radicals, and alkylsulfinyl, where bothenantiomers of the alkylsulfinyl group are encompassed, alkylsulfonyl,alkylphosphinyl, alkylphosphonyl and, in the case of cyclic radicals(=“cyclic parent body”), also alkyl, haloalkyl, alkylthioalkyl,alkoxyalkyl, optionally substituted mono- and dialkylaminoalkyl andhydroxyalkyl.

In the term “substituted radicals” such as substituted alkyl etc., aswell as the specified saturated hydrocarbon-containing radicals,corresponding unsaturated aliphatic and aromatic radicals are includedas substituents, such as optionally substituted alkenyl, alkynyl,alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, alkenyloxycarbonyl,alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono- anddialkenylaminocarbonyl, mono- and dialkynylaminocarbonyl, mono- anddialkenylamino, mono- and dialkynylamino, trialkenylsilyl,trialkynylsilyl, optionally substituted cycloalkenyl, optionallysubstituted cycloalkynyl, phenyl, phenoxy etc. In the case ofsubstituted cyclic radicals with aliphatic moieties in the ring, alsoencompassed are cyclic systems with those substituents which are bondedto a double bond on the ring, e.g. are substituted with an alkylidenegroup such as methylidene or ethylidene or an oxo group, imino group orsubstituted imino group.

The unsubstituted or substituted radicals in each case can be branchedor unbranched. Thus, for example, a radical referred to as “C₄-alkyl”encompasses, as well as the unbranched butyl radical, all further C₄isomers, including tert-butyl.

If two or more radicals form one or more rings, then these may becarbocyclic, heterocyclic, saturated, partially saturated, unsaturated,for example also aromatic and optionally further substituted. The fusedrings are preferably 5- or 6-membered rings, particular preference beinggiven to benzo-condensed cycles.

The core of the process according to the invention consists in thereaction of the starting materials of formula (1) and (2) in thepresence of bases which are characterized in that they do not decomposein the presence of water and, moreover, do not release hydrogen (H₂)during the reaction.

Some very strong to medium-strength bases, such as, e.g. sodium hydride(NaH), react in water with decomposition and are therefore unsuitablefor industrial application. Bases having these disadvantages can only behandled safely on a laboratory scale. For industrial application, strongbases, such as NaH, are therefore unsuitable.

In the reaction according to the invention the base used is preferably

-   -   potassium carbonate or sodium carbonate, and also    -   lithium hydroxide, sodium hydroxide, potassium hydroxide, barium        hydroxide or tert-alkylammonium hydroxide, and also    -   potassium phosphate (K₃PO₄), K₂HPO₄ or sodium phosphate, or    -   mixtures of at least two of the aforementioned bases.

Compared with strong bases, such as e.g. sodium hydride, the specifiedcarbonates, hydroxides and phosphates have the essential advantage thatthey are industrially more suitable since, in the case of their use, noequimolar amounts of hydrogen are formed and the specified weaker basesalso do not decompose in the presence of water.

Particularly preferred bases are potassium carbonate, sodium carbonate,sodium hydroxide, potassium hydroxide or an at least two-componentmixture consisting of at least one of the two carbonates: potassiumcarbonate and sodium carbonate, and also of at least one of the twohydroxides: potassium hydroxide or sodium hydroxide.

The four particularly preferred two-component mixtures thus relate tothe mixtures consisting of potassium carbonate and potassium hydroxide,potassium carbonate and sodium hydroxide, sodium carbonate and potassiumhydroxide, and also the mixture consisting of potassium carbonate andsodium hydroxide.

In addition, further mixtures which in each case comprise more than twoof the bases specified as being particularly preferred for the reactionare naturally conceivable.

Since the bases used according to the invention comprise water, and/orcan generate it or release it, but triazines (2) slightly hydrolyze inthe presence of water, it has to be regarded as surprising that thebases used according to the invention could prove suitable at all forachieving the object.

In a preferred embodiment of the process according to the invention, theradicals R^(1a) to R^(1d) in the compounds of formulae (3) and (1) areselected, independently of one another, from the group consisting ofhydrogen, fluorine, chlorine, bromine, iodine, and also from

-   (C₁-C₆)-alkyl, where the alkyl radical is branched or unbranched and    is unsubstituted or is substituted by one or more substituents    selected from the group consisting of fluorine and chlorine, and-   (C₃-C₇)-cycloalkyl, where the cycloalkyl radical is unsubstituted or    is substituted by one or more substituents selected from the group    consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkoxy.

In a particularly preferred embodiment, the radicals R^(1a) to R^(1d) inthe compounds of formulae (3) and (1) are selected, independently of oneanother, from the group consisting of fluorine, chlorine andtrifluoromethyl (CF₃), trifluoromethoxy (O—CF₃) and methoxy (O-Me).

In a very particularly preferred embodiment, the radical R^(1a) isfluorine or chlorine, i.e. the compounds of formulae (3) and (1) aresubstituted in the 7 position by fluorine (7-fluoro) or chlorine(7-chloro).

Very particular preference is likewise given to compounds of formulae(3) and (1) which are substituted in the 5 position by fluorine(5-fluoro), i.e. the radical R^(ic) is fluorine (see Example 5).

Furthermore, very particular preference is also given to compounds offormulae (3) and (1) which are substituted in the 7 position by fluorine(7-fluoro) and at the same time in the 5 position by fluorine(5-fluoro), i.e. the radicals R^(1a) and R^(1c) are fluorine (seeExample 3).

In a further particularly preferred embodiment, the radical R² informulae (3) and (1) is

-   -   hydrogen, or is in each case    -   unsubstituted methyl, ethyl and benzyl.

In a very particularly preferred embodiment, the nitrogen in the 1position of the compounds of formulae (3) and (1) is unsubstituted, i.e.the radical R² is hydrogen.

Within the scope of the invention, it is preferred that the reactionmixture from which the product of formula (3) where R³═H can beobtained, is rendered acidic by adding acid or a mixture of acids, inparticular hydrochloric acid, sulfuric acid, acetic acid or formic acid,in a technically relevant concentration, then the organic solvent iscompletely or partially distilled off and the residue is filtered. Thesolid product obtained in this way can be washed with suitable solvents.

Furthermore, it is particularly preferred that the reaction mixture fromwhich the product of formula (3) where R³═H can be obtained, is renderedacidic by adding hydrochloric acid or sulfuric acid of a technicallyrelevant concentration, acetic acid or formic acid, and additionally afurther organic solvent is added and the residue is filtered. The solidproduct obtained in this way can be washed with suitable solvents.

It is within the scope of the invention that, before or during theacidification, a suitable amount of antifoam is added to the reactionmixture which comprises products of formula (3) in order to reduceundesired foaming of the reaction mixture.

In a particularly preferred embodiment, the radicals R⁴ and R⁵ informulae (2) and (3) are, independently of one another, in each caseunsubstituted (C₁-C₄)-alkyl and unsubstituted (C₁-C₄)-alkoxy.

Very particular preference is given to compounds of formulae (2) and (3)in which the radicals R⁴ and R⁵ are, independently of one another, ineach case methoxy, ethoxy, methyl, ethyl.

In a particularly preferred embodiment, the leaving group X is achlorine.

An important aspect relates to the selection of the solvent in which thereaction is carried out. The reaction can be carried out in

-   -   a polar or    -   a nonpolar solvent, or in    -   a mixture of a polar or nonpolar solvent.

Nonpolar solvents which can be used are

-   -   haloalkanes, in particular dichloromethane or dichloroethane; or    -   aromatics, in particular toluene, xylene or chlorobenzene.

Polar organic solvents which can be used are

-   -   ketones, in particular acetone, butanone, 2-methylbutanone;    -   nitriles, in particular acetonitrile, butyronitrile,        isobutylnitrile;    -   amides, in particular N,N-dimethylformamide,        N,N-dimethylacetamide, formamide, N-methylformamide,        N-methylpyrrolidone;    -   sulfoxides and sulfones, for example dimethyl sulfoxide,        dimethyl sulphones, sulfolane;    -   ethers, in particular dioxane, 2-methyltetrahydrofuran, methyl        cyclopentyl ether, tert-butyl methyl ether or tetrahydrofuran;        or    -   esters, in particular ethyl acetate, n-butyl acetate or        isopropyl acetate.

The specified polar solvents can be used either on their own or inmixtures with other solvents, preferably with further polar organicsolvents or with water. In this connection, it is not excluded that thereaction also takes place in water as the sole solvent.

Particular preference is given to carrying out the process without usingwater as solvent.

The process according to the invention for the preparation of compoundsof formula (3) is based on the fact that the oxindole (1 equivalent) isreacted in a suitable solvent with the triazine component and the base.In this connection, the triazine component is preferably used in excess(1.1 to 1.4 equivalents, preferably 1.1 to 1.25 equivalents).

The base is used in equimolar amount or in excess. If R²═H, the base isused with 2 to 3 equivalents, preferably with 2.2 to 2.6 equivalents.

All reactants can be added to the reaction mixture either in pure formor premixed with one another or dissolved or suspended in a solvent or asolvent mixture.

For good product yields, it has been found that it may be advantageousto firstly react the oxindole with the base (total amount or partamount) in a suitable solvent, and then to add the triazine componentand, if appropriate, a further amount of the same or of a different baseor a mixture of different bases in one or more portions.

Another addition variant consists in initially introducing the oxindoleand the triazine component in a suitable solvent and adding the base, orthe mixture of different bases, in portions.

The addition of the reactants can take place in one or more portionsover a period of up to 24 hours, preferably up to 6 hours, in particular0.05 to 6 hours.

The reaction temperature is in the range from −20° C. to 150° C.,preferably in the range from −10° C. to 90° C.

If appropriate, the reaction can be carried out under pressure.

In the course of the reaction, further solvent can be added in order topermit better mixing of the reactants.

Depending on the reaction conditions used, the after-stirring timefollowing addition of all reactants is in the range up to 48 hours,preferably 0.05 to 24 hours.

Work-up and isolation of the desired product of formula (3) can takeplace in various ways, for example irrespective of which solvent is usedor whether the product is a solid or a liquid.

The invention also provides the compounds of formula (3),

which are obtainable for example by the process according to theinvention described above, and salts thereof (3″),

in which, in each case

-   R^(1a) to R^(1d), independently of one another, are selected from    the group consisting of hydrogen, fluorine, chlorine, bromine,    iodine, and also from-   (C₁-C₆)-alkyl, where the alkyl radical is branched or unbranched and    is unsubstituted or is substituted by one or more substituents    selected from the group consisting of fluorine, chlorine,    (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,-   (C₃-C₇)-cycloalkyl, where the cycloalkyl radical is unsubstituted or    is substituted by one or more substituents selected from the group    consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkoxy,-   (C₁-C₆)-alkoxy, where the alkoxy radical is branched or unbranched    and is unsubstituted or is substituted by one or more substituents    selected from the group consisting of fluorine, chlorine,    (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,-   (C₃-C₇)-cycloalkoxy, where the cycloalkoxy radical is unsubstituted    or is substituted by one or more substituents selected from the    group consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₁-C₄)-alkoxy,-   (C₁-C₆)-alkylthio, where the alkylthio radical is branched or    unbranched and is unsubstituted or is substituted by one or more    substituents selected from the group consisting of fluorine,    chlorine, (C₁-C₄)-alkyl or (C₁-C₄)-alkoxy,-   (C₃-C₇)-cycloalkylthio, where the cycloalkylthio radical is    unsubstituted or is substituted by one or more substituents selected    from the group consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₁-C₄)-alkoxy, and    -   phenyl or 1-naphthyl or 2-naphthyl or a five- or six-membered        heteroaromatic ring having 1 to 2 heteroatoms, where the        heteroatoms, independently of one another, are selected from the        group consisting of O or N and where the aryl or heteroaryl        radical is unsubstituted or is substituted by one or more        substituents selected from the group consisting of fluorine,        chlorine, bromine, iodine, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or        (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkylthio, and    -   R² is        -   hydrogen,        -   (C₁-C₆)-alkyl, where the alkyl radical is branched or            unbranched and is unsubstituted or is substituted by one or            more substituents selected from the group consisting of            fluorine, chlorine, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl, or        -   benzyl, where the benzyl is unsubstituted or is substituted            by one or more substituents selected from the group            consisting of fluorine, chlorine, bromine, iodine, nitro,            (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl or            (C₁-C₄)-alkylthio and also from COOR^(a), in which R^(a) is            a (C₁-C₄)-alkyl, and —CONR^(b′)R^(b″) or —CONHR^(b″), in            which R^(b′) and R^(b″) are each independently of one            another a (C₁-C₄)-alkyl, where in each case two substituents            on the N atom together optionally form an unsubstituted or            substituted ring,    -   R³ is        -   hydrogen,    -   R⁴ and R⁵, independently of one another, are in each case        hydrogen,        -   (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or            is substituted by one or more substituents selected from the            group consisting of fluorine, chlorine, (C₁-C₄)-alkoxy or            (C₃-C₇)-cycloalkyl,        -   (C₁-C₆)-alkoxy, where the alkoxy radical is branched or            unbranched and is unsubstituted or is substituted by one or            more substituents selected from the group consisting of            fluorine, chlorine, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,            where, in the salts of formula (3″),    -   M is Li, Na, K, N(R^(c))₄, where R^(c)═H or C₁-C₆-alkyl, Cs, Ba,        Mg, Ca and Zn, and the number of counterions M⁺ is governed by        the particular charge, such that an overall neutral compound of        formula (3″) is formed.

The formulae (3) and (3″), if applicable, also include allstereoisomers, tautomers and/or polymorphous forms, and also saltsthereof.

Particular preference is given to compounds of the formulae (3) in whichR³ is H or methyl.

Compounds of the formulae (3) in which R³ is H are most preferred.

Compounds of the formulae (3) and (3″) and also the compounds of formula(3) prepared by the process according to the invention are suitable asintermediates for producing fine chemicals and active ingredients fromagriculture.

Compounds of formula (3) and (3″) are triazinyl-substituted oxindoles.In scheme 3 below, triazinyl-substituted oxindoles are referred to byformula (5-1).

Scheme 3 shows a novel multistage synthesis process, according to which,starting from a 3-(alkylsulfanyl)-1,3-dihydro-2H-indol-2-one of formula(7-1) in an overall five-stage reaction, anN-alkyl-N-[2-(1,3,5-triazine-2-ylcarbonyl)phenyl]alkanesulfonamide offormula (4-1) can be prepared, the herbicidal activity (see WO2007/031208 A2) and fungicidal activity (see WO 2006/008159 A1) of whichhas already been known for a relatively long time.

The multistage process for the preparation ofN-alkyl-N-[2-(1,3,5-triazin-2-ylcarbonyl)phenyl]alkanesulfonamides (4-1)consists of the following part steps:

-   -   Reduction of substituted or unsubstituted        3-(alkylsulfanyl)-1,3-dihydro-2H-indol-2-ones (7-1) to give        substituted or unsubstituted 1,3-dihydro-2H-indol-2-ones (6-1).        This process is possible on an industrial scale and is described        in the patent application with the application number EP        10162381.7.    -   Arylation of substituted or unsubstituted        1,3-dihydro-2H-indol-2-ones (6-1) to give triazinyl-substituted        oxindoles (5-1). This process is possible on an industrial scale        and is described in the present patent application.    -   Sulfonylation of triazinyl-substituted oxindoles (5-1) to give        N-sulfonyl-substituted 3-triazinyloxindoles (2-1). This process        is possible on an industrial scale and is described in the        patent application with the application number EP 111598751.    -   Oxidative ring-opening of N-sulfonyl-substituted        3-triazinyloxindoles (2-1) to give        2-(triazinylcarbonyl)sulfonanilides (1-1). This process is        possible on an industrial scale and is described in the patent        application with the application number DE 102011086382.6.    -   Alkylation of 2-(triazinylcarbonyl)sulfonanilides (1-1) to give        N-alkyl-N-[2-(1,3,5-triazin-2-ylcarbonyl)phenyl]alkanesulfonamides        (4-1). This process is described in the patent application with        the application number WO 2006/008159.

The novel multistage process shown in scheme 3 is distinguished from thepreviously known processes for the preparation ofN-alkyl-N-[2[(1,3,5-triazin-2-ylcarbonyl)phenyl]alkanesulfonamides (4-1)and 2-(triazinylcarbonyl)sulfonanilides (1-1) in that oxindole compoundsare used as starting materials and/or as intermediates. This has theadvantage that, compared to the previously known processes, it can becarried out on an industrial scale, and at the same time high yields canbe attained.

The practicability of the process summarized in scheme 3 is disclosed indetail below. The reduction, which in scheme 3 concerns the firstreaction step of the overall five-stage process has been treated belowas independent preliminary stage B). The process A) described in detailbelow thus encompasses the steps of arylation, sulfonylation, oxidationand alkylation.

-   A) process for the preparation of    N-alkyl-N-[2-(1,3,5-triazine-2-ylcarbonyl)phenyl]alkanesulfonamides    of formula (4-1)

-    in which-   R^(1a) to R^(1d), independently of one another, are selected from    the group consisting of hydrogen, fluorine, chlorine, bromine,    iodine, and also from-   (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or is    substituted by one or more substituents selected from the group    consisting of fluorine, chlorine, (C₁-C₄)-alkoxy or    (C₃-C₇)-cycloalkyl,-   (C₃-C₇)-cycloalkyl, where the cycloalkyl radical is unsubstituted or    is substituted by one or more substituents selected from the group    consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkoxy,-   (C₁-C₆)-alkoxy, where the alkoxy radical is unsubstituted or is    substituted by one or more substituents selected from the group    consisting of fluorine, chlorine, (C₁-C₄)-alkoxy or    (C₃-C₇)-cycloalkyl,-   (C₃-C₇)-cycloalkoxy, where the cycloalkoxy radical is unsubstituted    or is substituted by one or more substituents selected from the    group consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₁-C₄)-alkoxy,-   (C₁-C₆)-alkylthio, where the alkylthio radical is unsubstituted or    is substituted by one or more substituents selected from the group    consisting of fluorine, chlorine, (C₁-C₄)-alkyl or (C₁-C₄)-alkoxy,-   (C₃-C₇)-cycloalkylthio, where the cycloalkylthio radical is    unsubstituted or is substituted by one or more substituents selected    from the group consisting of fluorine, chlorine, (C₁-C₄)-alkyl or    (C₁-C₄)-alkoxy, and phenyl or 1-naphthyl or 2-naphthyl or a five- or    six-membered heteroaromatic ring having 1 to 2 heteroatoms, where    the heteroatoms, independently of one another, are selected from the    group consisting of O or N and where the aryl or heteroaryl radical    is unsubstituted or is substituted by one or more substituents    selected from the group consisting of fluorine, chlorine, bromine,    iodine, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl or    (C₁-C₄)-alkylthio, and-   R²″ is    -   (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or is        completely or partially substituted with fluorine, or    -   (C₃-C₇)-cycloalkyl, where the cycloalkyl radical is        unsubstituted or is completely or partially substituted with        fluorine,-   R⁴ and R⁵, independently of one another, are in each case hydrogen,    -   (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or is        substituted by one or more substituents selected from the group        consisting of fluorine, chlorine, (C₁-C₄)-alkoxy or        (C₃-C₇)-cycloalkyl,    -   (C₁-C₆)-alkoxy, where the alkoxy radical is branched or        unbranched and is unsubstituted or is substituted by one or more        substituents selected from the group consisting of fluorine,        chlorine, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,    -   and-   R⁸ is    -   (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or is        completely or partially substituted with fluorine,    -   (C₁-C₆)-cycloalkyl, (C₁-C₆)-alkenyl or (C₁-C₆)-alkoxylalkyl,        where each of the specified radicals is unsubstituted or is        completely or partially substituted with fluorine,    -   where-   a 1,3-dihydro-2H-indol-2-one of formula (6-1)

-    in which-   R^(1a) to R^(1d) are as defined for formula (4-1),-   R³ is hydrogen, and-   R⁷ is hydrogen, is reacted in a-   first step by    -   arylation to give a triazinyl-substituted oxindole of formula        (5-1)

-   -    in which    -   R^(1a) to R^(1d) and R⁴ and R⁵ are as defined for formula (4-1)        and R³ and R⁷ are as defined for formula (5-1),    -   and the arylation products of formula (5-1) are reacted in a        second step by    -   sulfonylation to give N-sulfonyl-substituted        3-triazinyloxindoles of formula (2-1)

-   -    in which    -   R^(1a) to R^(1d), R²″ and also R⁴ and R⁵ are as defined in        formula (4-1), and R³ is as defined for formula (5-1),    -   and the solfonylation products of formula (2-1) are reacted in a        third step by    -   oxidative ring opening to give a        2-(triazinylcarbonyl)sulfonanilide of formula (1-1)

-   -    in which        -   R^(1a) to R^(1d), R²″ and also R⁴ and R⁵ are as defined for            formula (4-1),    -   and the oxidation products of formula (1-1) are reacted in a        fourth step by    -   alkylation to give an        N-alkyl-N-[2-(1,3,5-triazin-2-ylcarbonyl)phenyl]alkanesulfonamide        of formula (4-1)

-   -    in which        -   R^(1a) to R^(1d), R^(2″), R⁴, R⁵ and R⁸ are as defined above            for formula (4-1),            where the alkylation reagent used is    -   X—R⁸, where X is chlorine, bromine or iodine, and R⁸ is as        defined above for formula (4-1), or    -   (R⁸)₂SO₄, in which R⁸ is as defined above for formula (4-1).

The sulfonylation takes place in the presence of

-   -   an imidazole base substituted in the 1 position, or    -   a base mixture which comprises at least one imidazole base        substituted in the 1 position.

Particularly preferred imidazole bases are 1-methyl-1H-imidazole,1-butyl-1H-imidazole or 1-benzyl-1H-imidazole, which can be usedindividually or in a mixture, the use of 1-methyl-1H-imidazole beingvery particularly preferred.

-   B) Process for the preparation of    N-alkyl-N-[2-(1,3,5-triazin-2-ylcarbonyl)phenyl]alkanesulfonamides    of formula (4-1) in which the compounds of formula (6-1) used as    starting material are prepared in a process step preceding the    process for the preparation of compounds of formula (4-1), where,    starting from a 3-(alkylsulfanyl)-1,3-dihydro-2H-indol-2-one of    formula (7-1),

-    in which-   R^(1a) to R^(1d) are as defined for formula (4-1),-   R³ is hydrogen,-   R⁷ is hydrogen, and-   R⁶ is an unsubstituted or substituted (C₁-C₁₄)-alkyl,    (C₃-C₇)-cycloalkyl, benzyl or a CH₂—C(O)O—(C₁-C₆)-alkyl,    is converted by    -   reduction to give a 1,3-dihydro-2H-indol-2-one (6-1)

in which

-   -   R^(1a) to R^(1d), R³ and R⁷ are as defined for formula (7-1).

During the reduction,

-   a) a compound of formula (7-1) is dissolved or suspended in a polar    solvent,-   b) a sulfur-containing salt is added to the solution or the    suspension, and-   c) the reaction mixture is heated under reflux at a temperature    which corresponds at most to the boiling temperature of the polar    solvent.

The particularly preferred sulfur-containing salts are sodium saltsselected from the group consisting of sodium bisulfite, sodium sulfite,sodium thionite, sodium dithionite and sodium thiosulfate.

As already mentioned, the herbicidal effect (see WO 2007/031208 A2) andfungicidal effect (see WO 2006/008159 A1) ofN-alkyl-N-[2-(1,3,5-triazin-2-ylcarbonyl)phenyl]alkanesulfonamides offormula (4-1) has been known for a relatively long time.

Consequently, it is demonstrated by scheme 3 and processes A) and B)that triazinyl-substituted oxindoles of formula (3) are suitable asintermediates for producing crop protection agents, in particularherbicides and fungicides.

The invention therefore also provides the use of the compounds offormulae (3) or salts thereof (3″) prepared according to the inventionfor producing active ingredients from agriculture or of intermediatesfor producing fine chemicals and active ingredients from agriculture,particularly crop protection agents.

Preference is given to the use of compounds of formulae (3) or saltsthereof (3″) as intermediates for producingN-[2-(1,3,5-triazin-2-ylcarbonyl)phenyl]alkyl-sulfonamides.

The examples below illustrate the invention in more detail without,however, limiting its subject matter to these examples.

In the examples below, quantitative data is by weight, unless otherwisespecifically defined (in the description, % by weight=percent by weightwas used analogously for this). For measurement units, physicalparameters and the like, customary abbreviations are used, for exampleh=hour(s), m.p.=melting point, I=liter, ml=milliliter, g=gram,min=minute(s), in vacuo=“in a vacuum”=under reduced pressure, oftheory=percent yield according to the theory.

Example 1 Preparation of3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-7-fluoro-1,3-dihydro-2H-indol-2-one

Variant A:

7-Fluoro-1,3-dihydro-2H-indol-2-one (100 g) is introduced as initialcharge in 600 ml of N,N-dimethylacetamide and cooled to ca. 0° C. withice/methanol cooling. A solution of potassium hydroxide (43.2 g) andpotassium carbonate (143 g) in 600 ml of water is added and the mixtureis briefly after-stirred. Then, 2-chloro-4,6-dimethoxy-1,3,5-triazine(140.8 g) is added and in each case 100 ml of water andN,N-dimethylacetamide are used for after-rinsing. The cooling bath isremoved, the mixture heats up to ca. 30° C. It is stirred for 18 hoursat room temperature. After adding 150 ml of toluene, dilute hydrochloricacid (ca. 700 ml) is used to adjust the pH to 3-4 and at the same timesome antifoam (Fluowet PL 80) is added. The solid is filtered off withsuction, washed three times with in each case 250 ml of water and twicewith in each case 250 ml of heptane and dried in vacuo at 55° C. Thisgives the title compound as solid in a purity of 96.6% (187.5 g, 95% oftheory).

LC-MS: M+H=291 (100%).

¹H NMR (400 MHz, DMSO-D₆): δ (ppm)=11.37 (s, 1H), 7.64 (d, 1H), 6.97(dt, 1H), 6.86 (dd, 1H), 4.05 (s, 6H).

Variant B:

7-Fluoro-1,3-dihydro-2H-indol-2-one (50 g) is introduced as initialcharged in 400 ml of acetone and potassium hydroxide (21.5 g) is added.Then, 2-chloro-4,6-dimethoxy-1,3,5-triazine (70.06 g) is added, followedby rinsing with 100 ml of acetone. The reaction mixture is stirred atreflux for one hour, the heating bath is removed and potassium hydroxide(21.5 g) is added in portions. The mixture is then stirred for a furthertwo hours at reflux. The mixture is cooled to 25° C., ten percentstrength hydrochloric acid (140 ml) is added, and the mixture is dilutedwith 250 ml of water and after-stirred for one hour. The solid isfiltered off with suction, washed twice with in each case 100 ml ofwater/acetone (3:1) and dried in vacuo at 50° C. This gives the titlecompound as solid in a purity of 96.2% (80.09 g, 81% of theory). The NMRsignals of the product agree with the signals of the product obtainedaccording to Variant A.

Variant C:

7-Fluoro-1,3-dihydro-2H-indol-2-one (12 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (16.5 g) are introduced as initialcharge at room temperature in 160 ml of formamide, and potassiumcarbonate (24.3 g) is added in three equal portions over the course of1.5 hours. The reaction mixture is after-stirred for 4-5 hours at roomtemperature. The mixture is added to 500 ml of water and adjusted to pH3 with dilute hydrochloric acid. The solid is filtered off with suctionand washed with water, then with acetonitrile, and dried in vacuo. Thisgives the title compound as solid in an HPLC purity of 98% area (93.0 g,80% of theory). The NMR signals of the product agree with the signals ofthe product obtained according to Variant A.

Variant D:

7-Fluoro-1,3-dihydro-2H-indol-2-one (60 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (94.6 g) are introduced as initialcharge in 315 ml of THF and cooled to 5° C. With ice cooling, a solutionof potassium hydroxide (58.1 g) in 105 ml of water is added over thecourse of 2 hours at an internal temperature of 0-15° C., and themixture is after-stirred for 4 hours. The solid is filtered off withsuction, washed with water (2×150 ml) and dried in vacuo. This gives thetitle compound as solid in a purity of 98.2% (21.1 g, 91% of theory).The NMR signals of the product agree with the signals of the productobtained according to Variant A.

Variant E:

7-Fluoro-1,3-dihydro-2H-indol-2-one (30 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (43.9 g) are introduced as initialcharge at 60° C. in acetonitrile, and sodium hydroxide (16.8 g) is addedin four equal portions over the course of 40 min. The mixture wasafter-stirred for a further 90 min at this temperature and then cooledto 40° C. Hydrochloric acid (20% strength, 42 g) and water (160 g) areadded. After a further 30 min, the resulting suspension was filtered andthe filter residue was washed with acetonitrile. Drying in vacuo (50°C., <200 mbar) gave the title compound as solid with an HPLC purity of96.9% (48.0 g; 85% of theory). The NMR signals of the product agree withthe signals of the product obtained according to Variant A.

Variant F:

7-Fluoro-1,3-dihydro-2H-indol-2-one (10 g; 1 eq.) is introduced asinitial charge in 100 ml of THF and 100 ml of N,N-dimethylformamide atroom temperature under nitrogen, and sodium hydride (2.63 g; 60% inmineral oil, 1 eq.) is added. The mixture is after-stirred for 30 minand 2-chloro-4,6-dimethoxy-1,3,5-triazine (4.72 g; 0.4 eq.) is added inone portion. The mixture is after-stirred for 10 min at 35° C. and for 2hours at 80° C. The mixture is cooled and concentrated by evaporation invacuo (50° C. bath temperature, 10 mbar). 200 ml of water are added tothe residue, and the pH is adjusted to 3-4 with hydrochloric acid. Theprecipitated solid is filtered off with suction; the filtrate comprisesvirtually no product according to HPLC. The filter residue is washedwith water (50 ml), stirred in water-moist form with 75 ml ofacetonitrile, filtered off with suction, after-washed with acetonitrileand dried in vacuo. This gives the title compound as solid in an HPLCpurity of 97% area (7.62 g; 39% of theory, based on the7-fluoro-1,3-dihydro-2H-indol-2-one used or 97% of theory, based on the2-chloro-4,6-dimethoxy-1,3,5-triazine used). The NMR signals of theproduct agree with the signals of the product obtained according toVariant A.

Variant G:

7-Fluoro-1,3-dihydro-2H-indol-2-one (10 g; 1 eq.) and2-chloro-4,6-dimethoxy-1,3,5-triazine (14.1 g; 1.2 eq.) are reactedanalogously to Example 1 Variant F. This gives the title compound assolid in an HPLC purity of 97% area (7.65 g; 39% of theory, based on the7-fluoro-1,3-dihydro-2H-indol-2-one used). The NMR signals of theproduct agree with the signals of the product obtained according toVariant A.

Variant H (procedure analogous to Organic Letters (2010) 2306 examplesin Table 4 (Supplement page S-12 General Procedure):

7-Fluoro-1,3-dihydro-2H-indol-2-one (2.5 g; 1 eq.),2-chloro-4,6-dimethoxy-1,3,5-triazine (3.5 g; 1.2 eq.) and caesiumcarbonate (5.6 g, 1 eq.) are introduced as initial charge undernitrogen, and 95 ml of N,N-dimethylformamide (water content<0.1%) areadded. The mixture is heated to 65° C. and stirred under nitrogen for 5hours at 65° C. HPLC analysis (detection at 210 nm, data in areapercent, solvent signal is not integrated) reveals 16%7-fluoro-1,3-dihydro-2H-indol-2-one, 19% of the title compound(3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-7-fluoro-1,3-dihydro-2H-indol-2-one),57% of a main secondary component (or of a mixture of two or more mainsecondary components) and further small secondary components. Themixture is cooled to room temperature and added to 200 ml of saturatedammonium chloride solution. Ethyl acetate is added until two clearphases are formed (in total 2900 ml), the phases are separated, and theorganic phase is washed with water (2×150 ml) and 150 ml of sodiumchloride solution and dried over magnesium sulfate. The solvent isremoved in vacuo, during which a solid precipitates out. The solid isfiltered off and washed with some ethyl acetate. This gives 1.92 g of amixture which, according to HPLC analysis (detection at 210 nm, data inarea percent), consists to 56% (22% of theory) of the title compound andto 43% of a secondary component. An LC-MS of the mixture reveals thepresence of the title compound (M+H=291) and of a secondary componentwith a mass of 429 (M+H=430), which is probably a diarylated product.The identity of the title compound present in the product mixture can beconfirmed by spiking the reaction mixture with authentic material,prepared as in Example 1 variant A, and comparing the UV absorptions,and also by NMR spectroscopy of the mixture.

The filtrate is concentrated by evaporation in vacuo, giving 3.6 g ofresidue, which still contains DMF. HPLC analysis (detection at 210 nm,data in area percent, solvent signal is not integrated) of the residuereveals 19% 7-fluoro-1,3-dihydro-2H-indol-2-one, 1% of the titlecompound, 68% of a mixture of two main secondary components and furthersmall secondary components. An LC-MS of the residue reveals the presenceof the title compound (M+H=291.4%) and two secondary components with amass of 429 (M+H=430, 19% and 49%), which are presumably diarylatedproducts.

Example 2 Preparation of3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-1,3-dihydro-2H-indol-2-one

Variant A:

1,3-Dihydro-2H-indol-2-one (3.0 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (7.52 g) are reacted analogouslyto Example 1 Variant C. This gives the title compound as solid in anHPLC purity of 91% area (4.79 g, 73% of theory).

LC-MS: M+H=273 (91.8%).

¹H NMR (400 MHz, DMSO-D₆): δ (ppm)=10.96 (s, 1H), 7.78-7.84 (m, 1H),6.95-7.04 (m, 3H), 4.04 (s, 6H).

Variant B:

1,3-Dihydro-2H-indol-2-one (0.80 g; 1 eq.) is introduced as initialcharge in 8 ml of THF and 8 ml of N,N-dimethylformamide at roomtemperature under nitrogen, and sodium hydride (0.24 g; 60% in mineraloil, 1 eq.) is added. The mixture is after-stirred for 30 min, and2-chloro-4,6-dimethoxy-1,3,5-triazine (0.42 g; 0.4 eq.) is added in oneportion. The mixture is after-stirred for 2 hours at room temperature.The mixture is cooled and concentrated by evaporation in vacuo (40° C.bath temperature). 25 ml of water are added to the residue andhydrochloric acid is used to adjust the pH to 3-4. The precipitatedsolid is filtered off with suction, the filtrate comprises virtually noproduct according to HPLC. The filter residue is washed with water,stirred in the water-moist state with 10 ml of acetonitrile and filteredoff with suction. This gives the title compound as solid in an HPLCpurity of 90% area (0.61 g; 34% of theory, based on the1,3-dihydro-2H-indol-2-one used, or 84% of theory, based on the2-chloro-4,6-dimethoxy-1,3,5-triazine used). The NMR signals of theproduct agree with the signals of the product obtained according toVariant A.

Variant C:

1,3-Dihydro-2H-indol-2-one (0.80 g; 1 eq.) and2-chloro-4,6-dimethoxy-1,3,5-triazine (1.27 g; 1.2 eq.) are reactedanalogously to Example 1 Variant F. This gives the title compound assolid in an HPLC purity of 78% area (0.59 g; 30% of theory, based on the1,3-dihydro-2H-indol-2-one used). The NMR signals of the product agreewith the signals of the product obtained according to Variant A.

Example 3 Preparation of3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-5,7-difluoro-1,3-dihydro-2H-indol-2-one

5,7-Difluoro-1,3-dihydro-2H-indol-2-one (1.69 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (2.13 g) are reacted analogouslyto Example 1 Variant A. This gives the title compound as solid in anHPLC purity of 93% area (2.82 g, 85% of theory).

LC-MS: M+H=309 (97%).

¹H NMR (400 MHz, DMSO-D₆): δ (ppm)=11.42 (s, 1H), 7.35 (dd, 1H), 6.86(dt, 1H), 4.04 (s, 6H).

Example 4 Preparation of3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-7-chloro-1,3-dihydro-2H-indol-2-one

7-Chloro-1,3-dihydro-2H-indol-2-one (101.5 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (152 g) are reacted analogously toExample 1 Variant A. This gives the title compound as solid in an HPLCpurity of 99% area (181.9 g, 97% of theory).

LC-MS: M+H=307 (96.7%).

¹H NMR (400 MHz, DMSO-D₆): 6 (ppm)=11.39 (s, 1H), 7.77 (d, 1H),6.98-7.06 (m, 2H), 4.05 (s, 6H).

Example 5 Preparation of3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-5-fluoro-1,3-dihydro-2H-indol-2-one

5-Fluoro-1,3-dihydro-2H-indol-2-one (10 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (15.5 g) are reacted analogouslyto Example 1 Variant A. This gives the title compound as solid in anHPLC purity of 92% area (19 g, 91% of theory).

LC-MS: M+H=291 (90%).

¹H NMR (400 MHz, DMSO-D₆): 6 (ppm)=11.06 (s, 1H), 7.53 (dd, 1H), 6.95(dd, 1H), 6.82 (dt, 1H), 4.06 (s, 6H).

Example 6 Preparation of3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-7-methoxy-1,3-dihydro-2H-indol-2-one

7-Methoxy-1,3-dihydro-2H-indol-2-one (1.24 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (1.84 g) are reacted analogouslyto Example 1 Variant A. This gives the title compound as solid in anHPLC purity of 87% area (1.04 g, 43% of theory).

LC-MS: M−H=301 (84%).

¹H NMR (400 MHz, DMSO-D₆): 6 (ppm)=11.36 (s, 1H), 7.52 (d, 1H), 6.96 (t,1H), 6.71 (d, 1H), 4.04 (s, 6H), 3.85 (s, 3H).

Example 7 Preparation of3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-5-methoxy-1,3-dihydro-2H-indol-2-one

5-Methoxy-1,3-dihydro-2H-indol-2-one (1.59 g) and2-chloro-4,6-dimethoxy-1,3,5-triazine (1.97 g) are reacted analogouslyto Example 1 Variant A. This gives the title compound as solid in anHPLC purity of 92% area (1.39 g, 53% of theory).

LC-MS: M+H=303 (94%).

¹H NMR (400 MHz, DMSO-D₆): 6 (ppm)=10.89 (s, 1H), 7.43 (d, 1H), 6.89 (d,1H), 6.61 (dd, 1H), 4.06 (s, 6H), 3.74 (s, 3H).

Example 8 Preparation of7-fluoro-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-1,3-dihydro-2H-indol-2-one

7-Fluoro-1,3-dihydro-2H-indol-2-one (3.05 g) and2-chloro-4-methoxy-6-methyl-1,3,5-triazine (6.59 g) are reactedanalogously to Example 1 Variant A. This gives the title compound assolid in an HPLC purity of 85% area (4.73 g, 73% of theory).

LC-MS: M+H=275 (72%).

¹H NMR (400 MHz, DMSO-D₆): δ (ppm)=11.02 (s, 1H), 7.59 (d, 1H),6.91-6.98 (m, 1H), 6.85 (t, 1H), 4.06 (s, 3H), 2.46 (s, 3H).

Example 9 Preparation of3-(4,6-diethoxy-1,3,5-triazin-2-yl)-7-fluoro-1,3-dihydro-2H-indol-2-one

7-Fluoro-1,3-dihydro-2H-indol-2-one (1.0 g) is introduced as initialcharge in 10 ml of N,N-dimethylacetamide. A solution of potassiumcarbonate (1.8 g) and potassium hydroxide (0.3 g) in 10 ml of water isadded and the mixture is briefly after-stirred. Then, a solution of2-chloro-4,6-diethoxy-1,3,5-triazine (3.0 g, ca. 50% purity) in 10 ml ofN,N-dimethylacetamide, and 10 ml of water are added. A solid separatesout from the clear yellow solution. The mixture is stirred at roomtemperature and further 2-chloro-4,6-diethoxy-1,3,5-triazine (1 g, ca.50% purity) is added in two portions after 2 and 18 hours. The mixtureis stirred for a further 3 hours at 30° C., admixed with 10 ml oftoluene, adjusted to pH 1-2 with hydrochloric acid (10%) andafter-stirred for 30 min. The solid is filtered off with suction, washedtwice alternately with water and heptane and dried. This gives the titlecompound as solid in an HPLC purity of 99% area (1.53 g, 72% of theory).

LC-MS: M+H=319 (86%).

¹H NMR (400 MHz, DMSO-D₆): δ (ppm)=11.3 (s, 1H), 7.59 (d, 1H), 6.96 (dd,1H), 6.93-7.00 (m, 1H), 4.50 (q, 4H), 1.37 (t, 6H).

Example 10 Preparation of2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)oxy]-3-phenyl-1H-indol (ProcedureAnalogous to Organic Letters (2010) 2306 examples in Table 4 (Supplementpage S-12 General Procedure)

3-phenyl-1,3-dihydro-2H-indol-2-one (0.25 g; 1 eq.),2-chloro-4,6-dimethoxy-1,3,5-triazine (0.20 g; 1 eq.) and caesiumcarbonate (0.37 g, 1 eq.) are introduced as initial charge, and 20 ml ofN,N-dimethylformamide (water content<0.1%) are added. The mixture isstirred for 90 min at 23° C. HPLC analysis (detection at 210 nm, data inarea percent, solvent signal is not integrated) reveals 3%3-phenyl-1,3-dihydro-2H-indol-2-one, 1.5%2-chloro-4,6-dimethoxy-1,3,5-triazine, 68% of a main product and smallsecondary components. The mixture is added to 100 ml of water andadjusted to pH 4 with dilute hydrochloric acid. The precipitated solidis filtered off and washed with water. This gives a mixture which,according to HPLC analysis (detection at 210 nm, data in area percent),consists to 71% of a main product (0.37 g, 66% of theory). 100 mg of themixture are purified by column chromatography (eluant ethyl acetate andn-heptane 1:1) and the combined product fractions are concentrated byevaporation in vacuo. This gives the reaction product as a colorlesssolid in an HPLC purity of 93% area. Structural elucidation by 2D-NMRshows that it is not the product arylated in the 3 position(3-(4,6-dimethoxy-1,3,5-triazin-2-yl)-3-phenyl-1,3-dihydro-2H-indol-2-one),but the O-arylated product(2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)oxy]-3-phenyl-1H-indol).

LC-MS: M+H=349 (96%).

¹H-NMR (600 MHz, CDCl₃): δ (ppm)=8.95 (s, broad, 1H), 7.82 (d, 1H), 7.65(dd, 2H), 7.41 (t, 2H), 7.37 (d, 1H), 7.24 (q, 2H), 7.19 (t, 1H), 3.98(s, 6H).

The invention claimed:
 1. A process for preparing a compound of formula(3)

in which R^(1a) to R^(1d), independently of one another, are selectedfrom the group consisting of hydrogen, fluorine, chlorine, bromine,iodine, and also from (C₁-C₆)-alkyl, where the alkyl radical isunsubstituted or is substituted by at least one substituent selectedfrom the group consisting of fluorine, chlorine, (C_(i)-C₄)-alkoxy or(C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkyl, where the cycloalkyl radical isunsubstituted or is substituted by at least one or more substituentselected from the group consisting of fluorine, chlorine, (C₁-C₄)-alkylor (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkoxy, (C₁-C₆)-alkoxy, where thealkoxy radical is unsubstituted or is substituted by at least onesubstituent selected from the group consisting of fluorine, chlorine,(C₁-C₄)-alkoxy or (C₃-C₇) -cycloalkyl, (C₃-C₇)-cycloalkoxy, where thecycloalkoxy radical is unsubstituted or is substituted by at least onesubstituent selected from the group consisting of fluorine, chlorine,(C₁-C₄)-alkyl or (C₁-C₄) -alkoxy, (C₁-C₆)-alkylthio, where the alkylthioradical is unsubstituted or is substituted by at least one substituentselected from the group consisting of fluorine, chlorine, (C₁-C₄)-alkylor (C₁-C₄) -alkoxy, and also from (C₃-C₇)-cycloalkylthio, where thecycloalkylthio radical is unsubstituted or is substituted by at leastone substituent selected from the group consisting of fluorine,chlorine, (C₁-C₄)-alkyl or (C₁-C₄)-alkoxy, and also from phenyl or1-naphthyl or 2-naphthyl or a five- or six-membered heteroaromatic ringcomprising from 1 to 2 heteroatoms, where said heteroatoms,independently of one another, are selected from the group consisting ofO or N and where the aryl or heteroaryl radical is unsubstituted or issubstituted by at least one substituent selected from the groupconsisting of fluorine, chlorine, bromine, iodine, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkylthio, and R² ishydrogen, (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or issubstituted by at least one substituent selected from the groupconsisting of fluorine, chlorine, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,or benzyl, where the benzyl is unsubstituted or is substituted by atleast one substituents selected from the group consisting of fluorine,chlorine, bromine, iodine, nitro, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or(C₃-C₇)-cycloalkyl or (C₁-C₄)-alkylthio and also from COOR^(a), in whichR^(a) is a (C₁-C₄)-alkyl, and —CONR^(b′)R^(b″) or —CONHR^(b″), in whichR^(b′) and R^(b″) are each independently of one another a (C₁-C₄)-alkyl,where in each case two substituents on the N atom together optionallyform an unsubstituted or substituted ring, R³ is hydrogen, R⁴ and R⁵,independently of one another, are in each case hydrogen, (C₁-C₆)-alkyl,where the alkyl radical is unsubstituted or is substituted by at leastone substituent selected from the group consisting of fluorine,chlorine, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl, (C₁-C₆)-alkoxy, wherethe alkoxy radical is unsubstituted or is substituted by at least onesubstituent selected from the group consisting of fluorine, chlorine,(C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl, said process comprising reactingan oxindole (1)

 in which R^(1a) to R^(1d) and R² and R³ are as defined in formula (3),in a solvent with a triazine (2)

 in which R⁴ and R⁵ are as defined in formula (3), and X, as leavinggroup, is Cl, Br, I, alkylsulfonyl, (alkylsulfonyl)oxy,haloalkylsulfonyl, phenylsulfonyl or toluene-4-sulfonyl, which comprisescarrying out the reaction in the presence of potassium carbonate orsodium carbonate, lithium hydroxide, sodium hydroxide, potassiumhydroxide, barium hydroxide or tert-alkylammonium hydroxide, potassiumphosphate (K₃PO₄), potassium hydrogenphosphate (K₂HPO₄) or sodiumphosphate or in a mixture thereof.
 2. The process for preparing acompound of formula (3) as claimed in claim 1, wherein R^(1a) to R^(1d),independently of one another, are selected from the group consisting ofhydrogen, fluorine, chlorine, bromine, iodine, and also from(C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or issubstituted by at least one substituent selected from the groupconsisting of fluorine and chlorine, and (C₃-C₇)-cycloalkyl, where thecycloalkyl radical is unsubstituted or is substituted by at least onesubstituent selected from the group consisting of fluorine and chlorine,(C₁-C₄)-alkyl or (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkoxy.
 3. The processfor preparing a compound of formula (3) as claimed in claim 2, whereinR^(1a) to R^(1d), independently of one another, are selected from thegroup consisting of fluorine, chlorine, trifluoromethyl,trifluoromethoxy and methoxy.
 4. The process for preparing a compound offormula (3) as claimed in claim 3, wherein R^(1a) is fluorine orchlorine.
 5. The process for preparing a compound of formula (3) asclaimed in claim 1, wherein R² is hydrogen, or is in each caseunsubstituted methyl, ethyl and benzyl.
 6. The process for preparing acompound of formula (3) as claimed in claim 5, wherein R² is hydrogen.7. The process for preparing a compound of formula (3) as claimed inclaim 1, wherein R⁴ and R⁵, independently of one another, areunsubstituted (C₁-C₄)-alkyl, and unsubstituted (C₁-C₄)-alkoxy.
 8. Theprocess for preparing a compound of formula (3) as claimed in claim 1,wherein X is chlorine.
 9. The process for preparing a compound offormula (3) as claimed in claim 1, wherein reaction of startingmaterials is carried out in a polar or a nonpolar solvent, or a mixturethereof.
 10. The process for preparing a compound of formula (3) asclaimed in claim 1, wherein reaction takes place under anhydrousconditions in presence of said base.
 11. The process for preparing acompound of formula (3) as claimed in claim 1, wherein from 1.1 to 1.4equivalents of the triazine (2) are added to one equivalent of theoxindole (1).
 12. The process for preparing a compound of formula (3) asclaimed in claim 1, wherein addition of starting materials takes placein one portion or equally dosed over a period of up to 24 hours.
 13. Theprocess for preparing a compound of formula (3) as claimed in claim 1,wherein reaction of starting materials is carried out at a temperaturein a range from −20° to 150° C.
 14. A compound of formula (3)

or a salt thereof (3″)

in which R^(1a) to R^(1d), independently of one another, are selectedfrom the group consisting of hydrogen, fluorine, chlorine, bromine,iodine, and also from (C₁-C₆)-alkyl, where the alkyl radical isunsubstituted or is substituted by at least one substituent selectedfrom the group consisting of fluorine, chlorine, (C₁-C₄)-alkoxy or(C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkyl, where the cycloalkyl radical isunsubstituted or is substituted by at least one substituent selectedfrom the group consisting of fluorine, chlorine, (C₁-C₄)-alkyl or(C₃-C₇) -cycloalkyl or (C₁-C₄)-alkoxy, (C₁-C₆)-alkoxy, where the alkoxyradical is unsubstituted or is substituted by at least one substituentselected from the group consisting of fluorine, chlorine, (C₁-C₄)-alkoxyor (C₃-C₇) -cycloalkyl, (C₃-C₇)-cycloalkoxy, where the cycloalkoxyradical is unsubstituted or is substituted by at least one substituentselected from the group consisting of fluorine, chlorine, (C₁-C₄)-alkylor (C₁-C₄) -alkoxy, (C₁-C₆)-alkylthio, where the alkylthio radical isunsubstituted or is substituted by at least one substituent selectedfrom the group consisting of fluorine, chlorine, (C₁-C₄)-alkyl or(C₁-C₄) -alkoxy, (C₃-C₇)-cycloalkylthio, where the cycloalkylthioradical is unsubstituted or is substituted by at least one substituentselected from the group consisting of fluorine, chlorine, (C₁-C₄)-alkylor (C₁-C₄)-alkoxy, and also from phenyl or 1-naphthyl or 2-naphthyl or afive- or six-membered heteroaromatic ring comprising from 1 to 2heteroatoms, where said heteroatoms, independently of one another, areselected from the group consisting of O or N and where the aryl orheteroaryl radical is unsubstituted or is substituted by at least onesubstituents selected from the group consisting of fluorine, chlorine,bromine, iodine, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl or(C₁-C₄)-alkylthio, and R² is hydrogen, (C₁-C₆)-alkyl, where the alkylradical is unsubstituted or is substituted by at least one substituentselected from the group consisting of fluorine, chlorine, (C₁-C₄)-alkoxyor (C₃-C₇)-cycloalkyl, or benzyl, where the benzyl is unsubstituted oris substituted by at least one substituent selected from the groupconsisting of fluorine, chlorine, bromine, iodine, nitro, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl or (C₁-C₄)-alkylthio and also fromCOOR^(a), in which R^(a) is a (C₁-C₄)-alkyl, and —CONR^(b′)R^(b″) or—CONHR^(b″), in which R^(b′) and R^(b″) are each independently of oneanother a (C₁-C₄)-alkyl, where in each case two substituents on said Natom together optionally form an unsubstituted or substituted ring, R³is hydrogen, R⁴ and R⁵, independently of one another, are in each casehydrogen, (C₁-C₆)-alkyl, where the alkyl radical is unsubstituted or issubstituted by at least one substituent selected from the groupconsisting of fluorine, chlorine, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,(C₁-C₆)-alkoxy, where the alkoxy radical is unsubstituted or issubstituted by at least one substituent selected from the groupconsisting of fluorine, chlorine, (C₁-C₄)-alkoxy or (C₃-C₇)-cycloalkyl,where, in said salt of formula (3″), M is Li, Na, K, N(R^(c))₄, whereR^(c=H or C) ₁-C₆ alkyl, Cs, Ba, Mg, Ca and Zn, and number of counterions M⁺is governed by a particular charge such that an overall neutralcompound of formula (3″) is formed.